Method of use of epoxy-containing cycloaliphatic acrylic polymers as orientation control layers for block copolymer thin films

ABSTRACT

Disclosed herein is a method of controlling the orientation of microphase-separated domains in a block copolymer film, comprising forming an orientation control layer comprising an epoxy-containing cycloaliphatic acrylic polymer on a surface of a substrate, irradiating and/or heating the substrate to crosslink the orientation control layer, and forming a block copolymer assembly layer comprising block copolymers which form microphase-separated domains, on a surface of the orientation control layer opposite the substrate. The orientation control layer can be selectively cross-linked to expose regions of the substrate, or the orientation control layer can be patterned without removing the layer, to provide selective patterning on the orientation control layer. In further embodiments, bilayer and trilayer imaging schemes are disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of the followingco-pending application, which is assigned to the same assignee as thisapplication, International Business Machines Corporation of Armonk, N.Y.The below listed application is hereby incorporated herein by referencein its entirety: U.S. patent application Ser. No. 12/013,444, filed Jan.12, 2008.

TRADEMARKS

IBM® is a registered trademark of International Business MachinesCorporation, Armonk, N.Y., U.S.A. Other names used herein may beregistered trademarks, trademarks or product names of InternationalBusiness Machines Corporation or other companies.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to methods of use of orientation controlcompositions to impart controlled orientation of microdomains in filmsof block copolymers subsequently disposed on the orientation controllayer.

2. Description of Background

Block copolymers are well known self-assembly systems, which formperiodic microphase-separated domains (also referred to herein as both“microdomains” and “domains”) to minimize total free energy. Thin filmsof block copolymers provide spatial chemical contrast at thenanometer-scale (FIG. 1A) and, therefore, they have been used as analternative low-cost nanopatterning material for generating periodicnanoscale structures. For example, lamellar forming block copolymers canalign their domains either parallel (FIG. 1B) or perpendicularly (FIG.1C) to the surface of a substrate surface. The perpendicularly orientedlamellae provide nanoscale line patterns, while there is no surfacepattern created by parallel oriented lamellae. Where lamellae formparallel to the plane of the substrate, one lamellar phase forms a firstlayer at the surface of the substrate (in the x-y plane of thesubstrate), and another lamellar phase forms an overlying parallel layeron the first layer, so that no lateral patterns of microdomains and nolateral chemical contrast form when viewing the film along theperpendicular (z) axis. When lamellae form perpendicular to the surface,the perpendicularly oriented lamellac provide nanoscale line patterns.Therefore, to form a useful pattern, control of the orientation of theself-assembled microdomains in the block copolymer is necessary. Withoutexternal orientation control, thin films of block copolymers tend toself-organize into randomly oriented nanostructures (FIG. 1D) orundesired morphologies, which are of no use for nanopatterning becauseof the random nature of the features.

Orientation of block copolymer microdomains can been obtained by guidingthe self-assembly process with an external orientation biasing methodsuch as by use of a mechanical flow field, electric field, temperaturegradient, or by the influence of surface interaction by use of a surfacemodification layer, with the layer of block copolymer. Of these, use ofa surface modification layer for orientation control is relativelystraightforward to integrate into a spin-casting or other film-formingmanufacturing process, and is therefore desirable. Random copolymerbrushes, thermally cross-linked random copolymers, and self-assembledmonolayers have each been used as the basis of an orientation controllayer to induce preferential orientation in block copolymer thin films.

While surface modification methods can be readily integrated intomanufacturing processes, each has limits to its utility. Polymer brushesare difficult to tune to the desired thickness and surface energy, andrequire reactive precursors. Additional rinse steps are often requiredto remove non-bound material. The composition of random copolymer brushlayers must be tuned precisely to afford a neutral surface. This can beachieved by randomly copolymerizing two monomers, for example the samemonomers used in a block copolymer of interest, in a precise ratio.However, many otherwise useful block copolymers (i.e., those that canform microdomains) exist for which it is unfeasible to synthesize randomcopolymers of repeating units of each block, for example because ofdifferent required polymerization mechanisms. End-groupfunctionalization of polymers, or copolymerization with a thirdfunctionalized monomer, have been used to provide grafting sites.However, grafting efficiency is typically poor, requires impracticallylong annealing times, and is compatible with only a limited range ofsubstrates [See e.g., P. Mansky, Y. Liu, E. Huang, T. P. Russell, C.Hawker, “Controlling polymer surface interaction with random copolymerbrushes”, Science, 275, 1458, (1997).] Thermally crosslinkableunderlayers based on, for example, vinyl benzocyclobutene has been foundto resolve some of these issues, but often require extended thermal curesteps. [See e.g., Du Yeol Ryu, Kyusoon Shin, Eric Drockenmuller Craig J.Hawker, and Thomas P. Russell “A generalized approach to modification ofsolid surfaces” Science, 308, 236, (2005)]. Photopatternable underlayersbased on random copolymers of the monomers of the block copolymer withan appropriate functional monomer, for example, monomers having azide,glycidyl or acryloyl groups, have been used but provide relatively lowcross-linking efficiency (as measured by lengthy exposure times and/orlengthy bake/anneal steps) and can further require an extra rinse stepto remove non-crosslinked materials. [See e.g., Joona Bang, Joonwon Bae,Peter Löwenhielm, Christian Spiessberger, Susan A. Given-Beck, Thomas P.Russell, and Craig J. Hawker, “Facile routes to patterned surfaceneutralization layers for block copolymer lithography”, AdvancedMaterials, vol. 19, p. 4552 (2007); Eungnak Han, Insik In, Sang-MinPark, Young-Hye La, Yao Wang, Paul F. Nealey, and Padma Gopalan,“Photopatternable imaging layers for controlling block copolymermicrodomain orientation”, Advanced Materials, vol. 19, pp. 4448 (2007)(epoxy groups in underlayers)].

SUMMARY OF THE INVENTION

The shortcomings of the prior art are overcome and additional advantagesare provided through the provision of an orientation control layer. Theorientation control layer is crosslinkable with moderate baketemperatures or irradiation in less than two minutes, and is furthercompatible with a wide variety of substrates.

In an embodiment, a method of controlling the orientation ofmicrophase-separated domains in a block copolymer film comprises (a)forming an orientation control layer comprising an epoxy-containingcycloaliphatic acrylic polymer over a surface of a substrate, (b)irradiating and/or heating to crosslink the orientation control layer,(c) forming a block copolymer assembly layer comprising block copolymerswhich form microphase-separated domains upon forming the block copolymerassembly layer, on a surface of the orientation control layer oppositethe substrate, and (d) removing at least one microphase-separated domainto generate a topographical pattern.

In another embodiment, a method of controlling the orientation ofmicrophase-separated domains in specific areas of a substrate coatedwith a block copolymer film, comprises (a) forming an orientationcontrol layer comprising an epoxy-containing cycloaliphatic acrylicpolymer over a surface of a substrate, (b) exposing the orientationcontrol layer pattern-wise with actinic radiation, EUV, or electronbeam, to form a pattern of exposed and unexposed regions of theorientation control layer, (c) heating the substrate to crosslink theorientation control layer in the exposed regions, (d) removinguncrosslinked orientation control layer material in the unexposedregions with a solvent to uncover the surface of the substrate in theunexposed regions, (e) optionally, heating the substrate having thepatterned crosslinked orientation control layer to remove residualsolvent, (f) forming a block copolymer assembly layer comprising blockcopolymers that form microphase-separated domains, on a surface of thepatterned crosslinked orientation control layer opposite the substrate,and (g) optionally annealing the substrate to induce pattern formationin the block copolymer layer, wherein lamellae form perpendicular to theplane of the substrate over the crosslinked orientation control layer,and wherein the lamellae form parallel to the plane of the substrateover the uncovered surface of the substrate.

In another embodiment, a method of controlling the orientation ofmicrophase-separated domains and the directional alignment of themicrophase-separated domains in a block copolymer film, comprises (a)forming an orientation control layer comprising an epoxy-containingcycloaliphatic acrylic polymer over a surface of a substrate, (b)heating to crosslink the orientation control layer, (c) optionally,rinsing the orientation control layer with a solvent, (d) optionally,heating the substrate to remove residual solvent, (e) exposing theorientation control layer pattern-wise with actinic radiation, EUV,x-ray, or electron beam, to form a pattern of exposed and unexposedregions of the orientation control layer, (f) optionally, rinsing thepatterned orientation control layer with a solvent, (g) optionally,heating the substrate having the patterned orientation control layer toremove residual solvent, (h) forming a block copolymer assembly layercomprising a block copolymer having at least one block that formsmicrophase-separated, domains on a surface of the patterned orientationcontrol layer opposite the substrate, and (i) annealing the substrate toinduce microphase-separated domains to form a pattern in the blockcopolymer layer; wherein the microphase-separated domains are lamellae,and wherein when a pitch of the pattern in the patterned orientationcontrol layer is at least 200% larger than the pitch of lamellae, thelamellae form parallel to the plane of the substrate over the exposedregion of the patterned orientation control layer, and formperpendicular to the plane of the substrate on the unexposed region ofpatterned orientation control layer.

In another embodiment, a method of controlling the orientation ofmicrophase-separated domains and the directional alignment of themicrophase-separated domains in a block copolymer film comprises (a)forming an orientation control layer comprising an epoxy-containingcycloaliphatic acrylic polymer over a surface of a substrate., (b)heating the substrate to cross link the orientation control layer, (c)optionally, rinsing the orientation control layer with a solvent, (d)optionally, heating the substrate to remove residual solvent, (e)exposing the orientation control layer pattern wise with actinicradiation, EUV, x-ray, or electron beam, to form a pattern of exposedand unexposed regions of the orientation control layer, (f) optionally,rinsing the patterned orientation control layer with a solvent, (g)optionally, heating the substrate having the patterned orientationcontrol layer to remove residual solvent, (h) forming a block copolymerassembly layer comprising a block copolymer having at least one blockthat forms microphase-separated domains on a surface of the patternedorientation control layer opposite the substrate, and (i) annealing thesubstrate to induce microphase-separated domains to form a pattern inthe block copolymer layer; wherein the microphase-separated domains arelamellae, and wherein when a pitch of the pattern in the patternedorientation control layer is about the same as a pitch of the pattern inthe block copolymer layer, the exposed region is preferentially wettedby one domain of the block copolymer and the unexposed region is wettedby the other domain(s) of block copolymer, and the block copolymer formsa spatial replica of the underlying patterned orientation control layer.

In further embodiments, at least one microphase-separated domain isselectively removed to generate a topographical pattern, followed bypattern transfer from the topographic pattern to the substrate by areactive ion etch process. In still further embodiments, bilayer andtrilayer imaging schemes comprising the above method are disclosed.

Additional features and advantages are realized through the techniquesof the present invention. Other embodiments and aspects of the inventionare described in detail herein and are considered a part of the claimedinvention. For a better understanding of the invention with advantagesand features, refer to the description and to the drawings.

TECHNICAL EFFECTS

As a result of the summarized invention, technically we have identifiedcompositions and methods that are useful in forming an orientationcontrol layer at the surface of a substrate that can provide orientationcontrol of microdomains in a block copolymer layer disposed thereon. Themethods as disclosed allow for formation of self-assembling preparationof nanoscale structural features, and directional control of thenanopatterned features, by sequential deposition of the orientationcontrol layer using conventional solution coating techniques, providinggreater control of the desired feature patterns, integrability intodifferent post-patterning processes useful for obtaining differenttopographies by substrate etch, and thereby obtaining reduced processingand cycle time in the fabrication of such structures, and for thepreparation of a wide variety of features in a wide variety ofcompositional or topographic substrates.

BRIEF DESCRIPTION OF THE DRAWINGS

The subject matter which is regarded as the invention is particularlypointed out and distinctly claimed in the claims at the conclusion ofthe specification. The foregoing and other objects, features, andadvantages of the invention are apparent from the following detaileddescription taken in conjunction with the accompanying drawings inwhich:

FIG. 1 illustrates schematic representations of: (A) lamellae-formingblock copolymers in which domains of different blocks are depicted; (B)a block copolymer thin film with lamellar domains oriented parallel tothe substrate, (C) a block copolymer thin film with lamellae domainsoriented perpendicular to the substrates; (D) an atomic force microscopy(AFM) image of an exemplary lamellae-forming poly(styrene-b-methylmethacrylate) (abbreviated “PS-b-PMMA”) film formed on a siliconsubstrate without orientation control;

FIG. 2 illustrates a schematic representation of an exemplaryorientation control method using an layer of the orientation controlmaterial;

FIG. 3 illustrates the structure of an exemplarypoly(epoxydicyclopentadienyl methacrylate-ran-styrene) crosslinkableorientation control material;

FIG. 4 illustrates the results of casting and annealing thin films ofPS-b-PMMA on a surface of different exemplary crosslinked orientationcontrol layer films, Substrate A (Sub. A), Substrate B (Sub. B), andSubstrate C (Sub. C), with different compositions, annealed attemperatures of 200° C. for 6 hours;

FIG. 5 illustrates the compatibility of crosslinked orientation controllayer compositions on different surfaces;

FIG. 6 illustrates an embodiment of a trilayer-type patterning processusing a thin layer of the orientation control material on top of ahardmask and a transfer layer disposed between surfaces of the substrateand the hardmask;

FIG. 7 illustrates an embodiment of a bilayer-type patterning processusing a patterned layer of block copolymer containing a highlyetch-resistant block, and a relatively thick (greater than 100 nm) layerof the orientation control material as a transfer layer;

FIG. 8 illustrates (A) a method of photopatterning the depositedcrosslinked orientation control layer on a substrate to achieveperpendicular orientation of the self-assembled domains only inspecified regions, and (B) atomic force microscope (AFM) images ofparallel-oriented PS-b-PMMA lamellae in an unexposed region, and (C)perpendicularly-oriented PS-b-PMMA lamellae on a deep UV exposed region;and

FIG. 9 illustrates (A) a method of patterning a crosslinked orientationcontrol layer to achieve patterned regions of neutrality to direct thex-y placement of self-assembled domains, and (B) an AFM image ofPS-b-PMMA lamellae with perpendicular orientation on electron-beampatterned poly(epoxydicyclopentadienyl methacrylate-ran-styrene) (30:70ratio of mole percentages of epoxydicyclopentadienyl methacrylate tostyrene) showing well-aligned PS-b-PMMA lamellae.

The detailed description explains the preferred embodiments of theinvention, together with advantages and features, by way of example withreference to the drawings.

DETAILED DESCRIPTION OF THE INVENTION

Disclosed herein is a method for generating a film of a crosslinkedorientation control layer from an epoxy-based crosslinkable orientationcontrol material that is compatible with a wide variety of surfaces, andmethods for controlling the orientation of microdomains formed in alayer comprising microdomain-forming block copolymers disposed on thecrosslinked orientation control layer. The composition comprisesepoxy-containing cycloaliphatic acrylic polymers, such aspoly(styrene-ran-epoxydicyclopentadienyl methacrylate), that can betuned to provide neutral surfaces for block copolymers. The orientationcontrol materials can desirably crosslink during subsequent processingwhile forming the orientation control layer.

Unexpectedly, it has been found that the orientation control materials,when coated on a substrate in a film-forming process, provide acrosslinked orientation control layer having a neutral surface energythat can be tuned to be compatible with a variety of microdomain-forminglayers comprising the block copolymer. To this end, the orientationcontrol layer can be adjusted compositionally for use and compatibilitywith a wide variety of substrates, and with a wide variety ofmicrodomain-forming block copolymers or block copolymer compositions,making the orientation control material useful in a number of differentprocesses for patterning a substrate. (i) In an embodiment, theorientation control layer can be patterned to uncover the underlyingsubstrate in the unexposed regions of the pattern and thereby to providedifferent orientation (e.g., parallel or perpendicular) of microdomainsin block copolymers formed over these regions. (ii) In anotherembodiment, the orientation control layer can have patterns imagedthereon which effect a chemical change in the exposed regions of theimaged pattern, the pattern having a pitch about the same of the pitchof the block copolymer, so that nanostructures in the block copolymeralign on the patterned orientation control layer, with one blockcopolymer domain aligned to the exposed region and the other aligned tothe unexposed region. (iii) In another embodiment, a bilayer imagingsystem is contemplated. (iv) In yet another embodiment, a trilayerimaging system is contemplated.

As used herein, “phase-separate” refers to the propensity of the blocksof the block copolymers to form discrete microphase-separated domains,also referred to as “microdomains” and also simply as “domains”. Theblocks of the same monomer aggregate to form periodic domains, and thespacing and morphology of domains depends on the interaction and volumefraction among different blocks in the block copolymer. Domains of blockcopolymers can form during applying, such as during a spin-casting step,during a heating step, or can be tuned by an annealing step. “Heating”,also referred to herein as “baking”, is a general process wherein thetemperature of the substrate and coated layers thereon is raised aboveambient temperature. “Annealing” can include thermal annealing, thermalgradient annealing, solvent vapor annealing, or other annealing methods.Thermal annealing, sometimes referred to as “thermal curing” can be aspecific baking process for fixing patterns and removing defects in thelayer of the block copolymer assembly, and generally involves heating atelevated temperature (e.g., about 200° C. to about 250° C.), for aprolonged period of time (e.g., several minutes to several days) at ornear the end of the film-forming process. Annealing, where performed,typically is used to reduce or remove defects in the layer of lateralmicrophase-separated domains.

The crosslinkable orientation control layer comprising the crosslinkableorientation control material is compatible with a wide variety ofsurfaces and methods for controlling the orientation ofmicrophase-separated domains of the block copolymer. The composition ofepoxy-containing cycloaliphatic acrylic polymers used as the orientationcontrol material can be tuned to provide a neutral surface for usefulmicrodomain-forming block copolymers such as, for example,poly(styrene-b-methyl methacrylate). These epoxy-containingcycloaliphatic acrylic polymers do not require the addition of anexternal crosslinking agent to afford a crosslinked product. While manyepoxy-containing cycloaliphatic acrylate or methacrylate monomers arehydrophilic, the cycloaliphatic epoxide-based methacrylates arerelatively hydrophobic. For example, it has been found that relativelyhydrophilic random copolymers of styrene and glycidyl methacrylate haveproven either too polar to be neutral to PS-b-PMMA, or to possessinsufficient glycidyl groups to afford robust crosslinked films. Inanother example, the surface neutralization layers disclosed by Gopalanet al. based on terpolymers of styrene, methyl methacrylate, andglycidyl methacrylate require relatively high molecular weights tooffset the very low glycidyl methacrylate content. Further, theresulting low crosslink density requires a rinse step to removeunreacted material. Therefore, the material of Gopalan exhibits behaviormore consistent with a graft copolymer layer than with a crosslinkedfilm.

In contrast, the hydrophobicity of the cycloaliphatic epoxide-basedacrylic monomers disclosed herein allows for the incorporation ofsufficient quantities of epoxy groups into the polymer to afford goodcrosslinking without making the material too polar to be neutral, evenwhen the polymer molecular weight is low (i.e., Mw<10,000 g/mol). Highlycrosslinked films are advantageous in that they do not require an extrarinsing step to remove uncrosslinked material, saving process time andcost. In addition the high crosslink density limits swelling orinterdiffusion of solvent or other components during subsequentprocesses, particularly during spin casting of the block copolymerlayer. After crosslinking, films of the cycloaliphatic epoxide-basedacrylic polymer compositions described herein for the orientationcontrol layer can be washed with highly solvating solvents such astoluene or propylene glycol monomethyl ether acetate ((PGMEA) butexhibit virtually no swelling or thickness loss. Because of theseproperties, this material can serve as an orientation control materialdespite the fact that it does not contain both of the repeatingstructures/monomers in the block copolymer of interest (such as forexample, both styrene and methyl methacrylate as found in PS-b-PMMA).The crosslinkable orientation materials are readily preparable at scaleusing conventional free radical polymerization methods, so that it isunnecessary to employ controlled free radical methods, “living”polymerization methods, or specialty initiators. Molecular weights andcompositions are readily tailored by controlling the polymerizationconditions (e.g., temperature, time, etc.) and feed ratios,respectively.

In an embodiment, a method of controlling the orientation ofmicrophase-separated domains in a film comprising a block copolymer,comprises (a) forming an orientation control layer comprising anepoxy-containing cycloaliphatic acrylic polymer as an orientationcontrol material, on a surface of a substrate. Forming the orientationcontrol layer comprises applying an orientation control compositioncomprising the epoxy-containing cycloaliphatic acrylic polymer and acasting solvent on a surface of the substrate. The method of applicationis not particularly limited, and can be accomplished by a processcomprising, for example, spin-casting, dip-coating, doctor blading,spray dispense, or other suitable coating method, which is compatiblewith the processes and equipment used in microelectronics fabricationassembly lines.

Solvents that can be used vary with the solubility requirements of theorientation control materials. Exemplary casting solvents includepropylene glycol monomethyl ether acetate (PGMEA), ethoxyethylpropionate, anisole, ethyl lactate, 2-heptanone, cyclohexanone, amylacetate, γ-butyrolactone (GBL) and the like. In an embodiment,specifically useful casting solvents include propylene glycol monomethylether acetate (PGMEA), γ-butyrolactone (GBL), or a combination of thesesolvents.

After application, the orientation control layer can be furtherinitially processed to remove the solvent. Spin casting (including spindrying) can in some embodiments suffice to form the layer and remove thesolvent. In other embodiments, the orientation control layer is baked atelevated temperature to remove solvent and condense the film. In anembodiment, baking the substrate having the orientation control layercan be done at a temperature of 70 to 150° C. for at least 20 seconds,specifically for 20 to 180 seconds.

In an embodiment, the orientation control composition, from which theorientation control layer is formed, comprises a polymer comprisingFormula (1), Formula (2), or a combination comprising at least one ofthese polymers, as the orientation control material:

wherein, in Formulas (1) and (2), R₁, R₂, R_(5′), and R₆ areindependently H, F, CF₃, or CH₃; R₃ is a substituted or unsubstitutedphenyl, naphthyl, or anthracyl group; R₄ and R₈ are independentlymonocyclic or polycyclic C₃₋₃₀ epoxy-containing groups, specificallyC₆₋₁₂ epoxy-containing groups; R₇ and R_(7′), are each independently aC₁₋₂₀ aromatic group or C₁₋₂₀ aliphatic group, and at least one of R₅and R₅′, or R₇ and R_(7′) are not identical; and in Formulas (1) and(2), where x and y are independently 0 to 98, z is 2 to 100, the sum ofmonomer mole percentages x+y+z is at least 85, specifically 85 to 100,and the ratio of mole percentages x+y to z is 0:100 to 98:2.

Useful monomers which provide the epoxy-containing cycloaliphaticfunctional group of R₄ and R₈ in Formulas 1 and 2 include monomersselected from the group consisting of 2,3-epoxycyclohexyl(meth)acrylate, (2,3-epoxycyclohexyl)methyl (meth)acrylate,5,6-epoxynorbornene (meth)acrylate, epoxydicyclopentadienyl(meth)acrylate, and combinations comprising at least one of theforegoing. A preferred monomer is epoxydicyclopentadienyl(meth)acrylate. Herein, where “(meth)acrylate” is used, either anacrylate or methacrylate is contemplated unless otherwise specified.

In an embodiment, the epoxy-containing cycloaliphatic acrylic basepolymer is a copolymer or terpolymer further comprising at least oneadditional monomer having a group R₃, R₅, R_(5′), R₇, R_(7′) in additionto the epoxy-containing monomer. Exemplary additional monomers includemethyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl(meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate,ethylcyclopentyl (meth)acrylate, methylcyclopentyl (meth)acrylate,dicyclopentyl (meth)acrylate, 2-hydroxy ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, hydroxy adamantyl (meth)acrylate, adamantyl(meth)acrylate, methyladamantyl (meth)acrylate, ethyladamantyl(meth)acrylate, phenyladamantyl (meth)acrylate, hydroxyadamantyl(meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate,gamma-butyrolactone (meth)acrylate, 5-methacryloxy-2,6-norbornanecarbolactone, 5-acryloxy-2,6-norbornane carbolactone,2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoroisopropyl(meth)acrylate, styrene, 4-methyl styrene, α-methyl styrene, 4-hydroxystyrene, 4-acetoxy styrene, ethylene, propylene, 1-butene,1,3-butadiene, vinyl acetate, dihydropyran, norbornene, maleicanhydride, or a combination comprising at least one of the foregoingadditional monomers.

In an exemplary embodiment, an epoxy containing base polymer usefulherein is poly(styrene-ran-epoxydicyclopentadienyl methacrylate), arandom copolymer of styrene and expoxydicyclopentadienyl methacrylate.

The epoxy-containing cycloaliphatic acrylic base polymer desirably has amolecular weight and polydispersity amenable to processing as disclosedherein, including casting. In an embodiment, the epoxy containingpolymer has a weight averaged molecular weight (Mw) of 1,500 to1,000,000 g/mol, specifically 3,000 to 250,000 g/mol, and morespecifically 5,000 to 80,000 g/mol. Similarly, the epoxy-containingcycloaliphatic acrylic polymer has a number averaged molecular weight(Mn) of 1,000 to 1,000,000, more specifically 2,000 to 250,000 g/mol,and still more specifically 3,000 to 70,000 g/mol. The epoxy-containingcycloaliphatic acrylic polymer can have a polydispersity (Mw/Mn) of 1.01to 6, and is not particularly limited. Molecular weight, both Mw and Mn,can be determined by any method used in the art, and is generallydetermined by gel permeation chromatography using a universalcalibration method, calibrated to polystyrene standards.

The composition of the orientation control layer can be adjusted byvarying the ratios and identities of the comonomers and by selecting thestructure of the cycloaliphatic group. In an exemplary embodiment, wherethe orientation control layer comprises a copolymer of styrene andepoxydicyclopentadienyl methacrylate, the composition is tunable byvarying the ratio of styrene to epoxydicyclopentadienyl methacrylate.For a range of exemplary epoxydicyclopentadienyl methacrylate-containingpolymer compositions, the surface will be neutral for lamellae-formingor cylinder-forming PS-B-PMMA diblock copolymers of as illustrated inFIG. 4. In FIG. 4, substrate A has an orientation control layercomprising poly(epoxydicyclopentadienyl methacrylate); substrate B hasan orientation control layer comprising poly(epoxydicyclopentadienylmethacrylate-ran-styrene) (90:10 mol/mol monomer ratio, respectively);and substrate C has an orientation control layer comprisingpoly(epoxydicyclopentadienyl methacrylate-ran-styrene) (80:20 mol/molmonomer ratio) respectively. In this case of substrates A-C, substrate Coffers a sufficiently neutral surface that the perpendicular orientationof the phase separated domains is stable even after 6 hours of annealingat 200° C.

Formulations may also contain basic additives as stabilizers,surfactants, and other additives known in the art to improve formulationstability and coating performance. Films may be formed by spin casting,dip-coating, doctor blading, or other film forming methods known in theart, although spin-casting is preferred due to its ready availability asa method in semiconductor fabs. Film thicknesses can be varied from lessthan 10 nanometers to several micrometers by controlling spin speed andthe solids content in the formulation.

In an embodiment, the orientation control composition also comprises anacid or acid generator comprising a thermal acid generator, photoacidgenerator, or a combination of thermal acid generator and photoacidgenerator. The epoxide groups crosslink the polymers when heated in thepresence of a strong acid catalyst (e.g. triflic acid). The acid can begenerated from blocked acid catalysts either via heat (thermal acidgenerators) or radiation (photoacid generator). Many such suitableacid-generating catalysts are known in the art. Exemplary acidgenerators include N-hydroxyphthalimide triflate, bis(4-1-butylphenyl)iodonium triflate, bis(4-t-butyl phenyl)iodoniumperfluoro-1-butanesulfonate, bis(4-t-butyl phenyl)iodoniumperfluoro-1-octanesulfonate, bis(phenyl)iodonium hexafluoroantimonate,N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, ora combination comprising at least one of the foregoing acid generators.

In an embodiment, the thermal and/or photoacid generator is present inan amount of 0.01 to 40 wt % based on the total weight of theorientation control composition, the additive is present in an amount of0.01 to 40 wt % of the total weight of the orientation controlcomposition, and the total solids of the orientation control compositioncomprising base polymer, thermal acid generator and/or photo-acidgenerator, and additive is 0.5 to 30 wt % based on the total weight ofthe orientation control composition including casting solvent.

The orientation control layer, after spin casting, is further processedby (b) heating the substrate to crosslink the orientation control layer.In (b), heating comprises baking the substrate having the orientationcontrol layer at a temperature of 100 to 250° C. for at least 30seconds, specifically 30 to 300 seconds. Treatment of the orientationcontrol layer at these temperatures can effectively crosslink thecomponents of the orientation control layer.

Solvent rinse of the orientation control layer can additionally beperformed to ensure no low molecular weight monomeric or oligomericspecies are present, prior to application of the block copolymerassembly composition. In an embodiment, the method further comprises (c)rinsing the orientation control layer with a solvent. Any solvent usedto rinse an organic layer can be removed to a low residual level (i.e.,less than 1 wt % of the film) prior to subsequent application.Accordingly, in another embodiment, the method can further comprise (d)heating the substrate to remove the residual solvent.

Next, in a further film forming operation, (e) a block copolymerassembly layer comprising block copolymers that formmicrophase-separated domains, is formed on a surface of the orientationcontrol layer opposite the substrate.

The block copolymer of the block copolymer assembly comprises blockscomprising one or more monomers, and at least two blocks in the blockcopolymer are compositionally, structurally, or both compositionally andstructurally non-identical. The block copolymer can be a diblockcopolymer, triblock copolymer, or multiblock copolymer. The blocksthemselves can be homopolymers or copolymers. Different kinds of blockcopolymers can be used in the block copolymer assembly, including anamphiphilic organic block copolymer, amphiphilic inorganic blockcopolymer, organic di-block copolymer, organic multi-block copolymer,inorganic-containing di-block copolymer, inorganic-containingmulti-block copolymer, linear block copolymer, star block copolymer,dendritic block copolymer, hyperbranched block copolymer, graft blockcopolymer, or a combination comprising at least one of the foregoingblock copolymers. Suitable inorganic constituents of theinorganic-containing polymers, monomers, molecules, and additivesinclude, for example, those based on silicon, germanium, iron, titanium,aluminum, or the like. Exemplary silicon- and germanium-containingmonomers and polymers can include those disclosed by H. Ito in “ChemicalAmplification Resists for Microlithography” Adv. Polym. Sci., vol. 172,pp. 37-245 (2005); exemplary metal containing monomers and polymersinclude those disclosed by Ian Manners in “Synthetic Metal-containingPolymers”, Wiley-VCH, 2004; exemplary silicon-containing molecules andadditives such as organosilicates include those disclosed by E. M.Freer, L. E. Krupp, W. D. Hinsberg, P. M. Rice, J. L. Hedrick, J. N.Cha, R. D. Miller, and H. C. Kim in “Oriented mesoporous organosilicatethin films”, Nano Letters, vol. 5, 2014 (2005); and exemplarymetal-containing molecules and additives include those disclosed byJinan Chai, Dong Wang, Xiangning Fan, and Jillian M. Buriak, “Assemblyof aligned linear metallic patterns on silicon”, Nature Nanotechnology,vol. 2, p. 500, (2007).

The blocks can be any appropriate microdomain-forming block that can becopolymerized with another, dissimilar block. Blocks can be derived fromdifferent polymerizable monomers, where the blocks can include but arenot limited to: polyolefins including polydienes, polyethers includingpoly(alkylene oxides) such as poly(ethylene oxide), poly(propyleneoxide), poly(butylene oxide), or random or block copolymers of these;poly((meth)acrylates), polystyrenes, polyesters, polyorganosiloxanes,polyorganogermanes, and the like.

In an embodiment, the blocks of the block copolymer comprise as monomersC₂₋₃₀ olefinic monomers, (meth)acrylate monomers derived from C₁₋₃₀alcohols, inorganic-containing monomers including those based on Fe, Si,Ge, Sn, Al, Ti, or a combination comprising at least one of theforegoing monomers. In a specific embodiment, exemplary monomers for usein the blocks can include, as the C₂₋₃₀ olefinic monomers, ethylene,propylene, 1-butene, 1,3-butadiene, isoprene, vinyl acetate,dihydropyran, norbornene, maleic anhydride, styrene, 4-hydroxy styrene,4-acetoxy styrene, 4-methylstyrene, or α-methylstyrene; and can includeas (meth)acrylate monomers derived from C₁₋₃₀ alcohols, methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth) acrylate,n-pentyl (meth)acrylate, isopentyl (meth)acrylate, neopentyl(meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate,isobornyl (meth)acrylate, or hydroxyethyl (meth)acrylate. Combinationsof two or more of these monomers can be used. Exemplary blocks which arehomopolymers can include blocks prepared using styrene (i.e.,polystyrene blocks), or (meth)acrylate homopolymeric blocks such aspoly(methylmethacrylate); exemplary random blocks include, for example,blocks of styrene and methyl methacrylate (e.g., poly(styrene-co-methylmethacrylate)), randomly copolymerized; and an exemplary alternatingcopolymer block can include blocks of styrene and maleic anhydride whichis known to form a styrene-maleic anhydride diad repeating structure dueto the inability of maleic anhydride to homopolymerize under mostconditions (e.g., poly(styrene-alt-maleic anhydride)). It will beunderstood that such blocks are exemplary and should not be consideredto be limiting.

Exemplary block copolymers that are contemplated for use in the presentmethod also include diblock copolymers such as poly(styrene-b-vinylpyridine), poly(styrene-b-butadiene), poly(styrene-b-isoprene),poly(styrene-b-methyl methacrylate), poly(styrene-b-alkenyl aromatics),poly(isoprene-b-ethylene oxide), poly(styrene-b-(ethylene-propylene)),poly(ethylene oxide-b-caprolactone), poly(butadiene-b-ethylene oxide),poly(styrene-b-t-butyl (meth)acrylate), poly(methylmethacrylate-b-t-butyl methacrylate), poly(ethylene oxide-b-propyleneoxide), poly(styrene-b-tetrahydrofuran),poly(styrene-b-isoprene-b-ethylene oxide), or a combination comprisingat least one of the foregoing block copolymers.

The block copolymer desirably has an overall molecular weight andpolydispersity amenable to further processing. In an embodiment, theblock copolymer has a weight-averaged molecular weight (Mw) of 3,000 to100,000 g/mol. Similarly, the block copolymer has a number averagedmolecular weight (Mn) of 1,000 to 60,000. The block copolymer can alsohave a polydispersity (Mw/Mn) of 1.01 to 6, and is not particularlylimited thereto. Molecular weight, both Mw and Mn, can be determined by,for example, gel permeation chromatography using a universal calibrationmethod, calibrated to polystyrene standards.

In an embodiment, forming the block copolymer assembly layer comprisesapplying a block copolymer composition comprising the block copolymerand a casting solvent, to a surface of the orientation control layeropposite the substrate. Applying can be accomplished by a processcomprising spin casting, dip coating, doctor blading, or spray dispense.

After applying, the substrate having the block copolymer and orientationcontrol layers can be baked at a temperature of 70 to 150° C. for atleast 20 seconds, specifically 20 to 180 seconds.

In addition, the block copolymer composition can comprise additionalcomponents selected from the group consisting of: additional polymers,including homopolymers, random copolymers, crosslinkable polymers, orinorganic-containing polymers; additives including small molecules,inorganic-containing molecules, surfactants, photoacid generators,thermal acid generators, quenchers, hardeners, cross-linkers, chainextenders, or a combination comprising at least one of the foregoing;and combinations comprising at least one of the foregoing, wherein oneor more of the additional components co-assemble with the blockcopolymer to form the block copolymer assembly layer.

In this way, an oriented block copolymer film is prepared by the abovemethod, wherein the microphase-separated domains comprise cylindricalmicrodomains oriented perpendicular to the surface of the orientationcontrol layer, or wherein the microphase-separated domains compriselamellar domains oriented perpendicularly to the surface of theorientation control layer.

During forming of the block copolymer assembly layer, the domains of theblock copolymer align perpendicular to the surface of the orientationcontrol layer. After coating a layer of block copolymers such aspoly(styrene-b-methyl methacrylate) and annealing, the domains of theblock copolymer will remain perpendicular to the neutral surface. Theorientation control layer can itself be formed on top of and crosslinkedto a variety of surfaces such as silicon, silicon oxide, siliconnitride, gold, and platinum and many other substrates, when baked in thepresence of acid (formed thermally from a thermal acid generator orphotochemically from a photoacid generator) as shown in FIG. 5. Hardmaskmaterials disposed on a substrate or substrate stack can be used as thesubstrate in the case a trilayer-type pattern transfer process.Alternatively, very thick orientation control layers can be formed whichcan serve as transfer layers if a bilayer-type pattern transfer processis desired, in which one of the blocks of the block copolymer hasperpendicular etch selectivity due inorganic-containing units or via aco-assembling additive.

A topographical pattern is then formed in the block copolymer film. In afilm comprising the block copolymer assembly comprising microdomains,those microdomains having a common composition can be selectivelyremoved by a suitable process such as wet or dry etch, development, orsolvent solubility, so that one microdomain comprising one kind of blockis selectively removed over another microdomain comprising another kindof block. Thus, in an embodiment, a microdomain of the block copolymerfilm is selectively removed to provide a topographical pattern. Thetopographical pattern can then be transferred to the substrate by asuitable subsequent etch process. In an embodiment, the topographicalpattern is generated by selectively etching a microdomain having ahigher Ohnishi number than the other microphase-separated domain(s) byan oxygen plasma etch.

The pattern forming method disclosed herein maybe used in an imagingscheme such as a bilayer or trilayer scheme, for high-resolutionpatterning of a substrate. In a bilayer scheme, the block copolymer ofthe block copolymer assembly layer has a block comprisinginorganic-containing monomers (such as silicon or germanium containingmonomers); or wherein the block copolymer assembly layer comprises, inaddition to the block copolymer, inorganic-containing polymers (such asgermanium-containing polymers or silicon-containing polymers),inorganic-containing molecules (such as silicon-containing orgermanium-containing molecules), which co-assemble with themicrophase-separated domains of the block copolymer to form the blockcopolymer assembly layer. The orientation control layer has, in anembodiment, a thickness of less than or equal to 100 nm.

The perpendicular orientation of the block copolymer domains isdesirable so the pattern can be readily transferred to the underlyingsubstrate by processes such as dry or wet chemical etching. Theperpendicular orientation of block copolymer domains can also generatelamellar and cylindrical morphologies with high-vertical aspect ratio.In some cases, the orientation control layer and block copolymers can becoated directly on the substrate of interest and the pattern transferreddirectly into the underlying substrate. However, in a specificembodiment, a trilayer pattern transfer scheme shown in FIG. 6 can beused. FIG. 6 shows (1) a block copolymer layer, disposed on theorientation control layer, in turn disposed on a surface of a hardmask,all of which are disposed in this order on a surface of an organicpattern transfer layer that is in contact with the substrate surface.The pattern is transferred (2) to the orientation control layer from themicrodomain-patterned block copolymer layer, then to the hardmask layer(3) by appropriate etch processes. Finally, the organic layers on thehardmask are removed, and the pattern transferred (4) to the relativelythick transfer layer from the patterned hardmask. The thin blockcopolymer pattern can be transferred first to the orientation controllayer, then into the hardmask layer, relying on differing etchresistance of the various segments of the block copolymer. In the caseof, for example, PS-b-PMMA, the relative etch rate selectivity in oxygenreaction ion etching is relatively small and the film is thin.Therefore, it is beneficial to have a thin orientation control layer(less than or equal to 20 nm) such that pattern fidelity is not lostwhile etching through the orientation control layer. The pattern can bedirectly transferred through the underlayer into the hardmask, oroptionally, one of the domains of the block copolymer can be removedbefore pattern transfer. Once the pattern is successfully transferredinto the hardmask, it can be transferred easily through the underlyingtransfer layer and then on into the substrate without difficulty.

Thus, in an embodiment, the substrate further comprises an underlayerdisposed on a surface of the substrate, and a hardmask disposed on asurface of the underlayer opposite the substrate, and wherein theorientation control layer is disposed on a surface of the hardmaskopposite the underlayer. In a further embodiment, the orientationcontrol layer has a thickness of less than or equal to 20 nm.

Block copolymers containing an inorganic group such as silicon orgermanium can be integrated into a bilayer-type patterning scheme (seeFIG. 7). FIG. 7 shows (1) a block copolymer layer with highlyetch-resistant microdomains, disposed on a relatively thick orientationcontrol layer acting as the organic pattern transfer layer, both ofwhich are disposed in this order on a surface of the substrate surface.The pattern is generated (2 a) in the block copolymer layer, andtransferred to the orientation control layer (2 b) by an appropriateetch process. The pattern in (2 a) can be established either by an etchor developing process, or optionally, the nascent pattern on theunetched or undeveloped block copolymer layer (1) can be etched throughboth the block copolymer layer and the orientation control layer to thesubstrate in a single etch process.

In this case, sufficient (or perpendicular) relative etch resistanceexists between the block copolymer segments such that etching through athick transfer layer can be achieved without loss of pattern fidelity.In this case, a thick coating (>100 nm) of crosslinked orientationcontrol underlayer can serve both as an orientation control layer and asan etchable pattern transfer layer during the subsequent patterntransfer process. The pattern can be directly transferred through thethick underlayer or, like in the trilayer scheme, one of the blockcopolymer domains may be removed beforehand. After pattern formation inthe block copolymer layer, pattern transfer to the orientation controllayer is effected by a reactive-ion plasma etch process.

The film forming method can further comprise annealing the substrate toinduce pattern formation in the block copolymer-layer. In an embodiment,annealing is by thermal annealing, and can be carried out at 80 to 300°C. for a time of 30 seconds to 20 hours. In a further embodiment, thepattern can be established by removing at least one domain to generate atopographical pattern or to transfer the pattern in the block copolymerto the subsequent layers.

In an embodiment, the ability to photochemically generate the acidrequired for crosslinking enables the patterning of the neutral surfaceon a substrate in an initial lithography step. In one example, acrosslinked film of the neutral underlayer would only be formed in theexposed regions. Subsequent casting and annealing of a block copolymeron the patterned surface would result in perpendicular orientation ofthe block copolymer domains only on the patterned neutral areas withparallel orientation in the non-neutral areas. This scheme is outlinedin FIG. 8. FIG. 8A shows photopatterning of an orientation controlunderlayer. A substrate is coated (1), then exposed (2) with a lightsource (flood exposure or stepper, using UV light) and photomask. Then,after post exposure processing including a post-exposure bake, rinse,and optionally a final bake, and development of the features, thepatterned orientation control layer (3) is then coated with a solutionof block copolymer (4), followed by spinning and baking to removesolvent and orient the microdomains to form a pattern (5) in which themicrodomains form perpendicularly (⊥) over the remaining orientationcontrol layer, and form parallel microdomains (∥) over the exposedregions of the substrate.

Thus, in an embodiment, a method of controlling the orientation ofmicrophase-separated domains in specific areas of a substrate coatedwith a block copolymer film, comprises (a) forming an orientationcontrol layer comprising an epoxy-containing cycloaliphatic acrylicpolymer over a surface of a substrate, (b) exposing the orientationcontrol layer pattern-wise with actinic radiation, EUV, or electronbeam, to form a pattern of exposed and unexposed regions of theorientation control layer, (c) heating the substrate to crosslink theorientation control layer in the exposed regions, (d) removinguncrosslinked orientation control layer material in the unexposedregions with a solvent to uncover the surface of the substrate in theunexposed regions, (e) optionally, heating the substrate having thepatterned crosslinked orientation control layer to remove residualsolvent, (f) forming a block copolymer assembly layer comprising blockcopolymers having at least two microphase-separated domains, on asurface of the patterned crosslinked orientation control layer oppositethe substrate, and (g) annealing the substrate to induce patternformation in the block copolymer layer, wherein the lamellae formperpendicular to the plane of the substrate over the crosslinkedorientation control layer, and wherein the lamellae form parallel to theplane of the substrate over the uncovered surface of the substrate.

In a further technique shown in FIG. 9, a blanket film of thecrosslinked orientation control layer can be patterned by subjecting itto various radiation (from deep ultraviolet, extreme ultraviolet, x-ray,ion, or electron beam sources). The patterned areas will becomenon-neutral and, in the best cases, develop an affinity for one of thesegments of the block copolymer. This patterning of selective andneutral surface domains affords the ability to not only controlperpendicular vs. parallel orientation but also x-y placement of theblock copolymer domains. Using the inventive compositions describedherein, well-aligned block copolymers such as, for example, PS-b-PMMAcan be achieved with, in an exemplary embodiment, an electron-beampatterned neutral underlayer. The method is shown in FIG. 9A.

FIG. 9A shows patterning on an orientation control layer. A substrate iscoated with the orientation control layer (1), then a nascent patternformed by selective exposure (2, top view) by DUV lithography or laserinterferometry, or by using radiation or other energetic patterningsource such as EUV, x-ray, e-beam, or ion beam, with a pattern maskwhere appropriate. The pitch of the patterned orientation control layeris about the same as the pitch of the block copolymer. The patternedorientation control layer (3) is then coated with a solution of blockcopolymer (3), followed by spinning and baking to remove solvent andorient the microdomains to form a pattern (4 a) in which themicrodomains form perpendicularly over the exposed regions of thesubstrate to provide a pattern (4 b, top view). Blocks with an affinityfor the exposed regions of the orientation control layer selectivelyform microdomains on the exposed regions and the other blocks formdomains on the adjacent unexposed regions. Therefore, the blockcopolymer domains align on the underlying patterns on the orientationcontrol layer and replicate the patterns. In another embodiment, notshown, the pitch of the pattern established in the orientation controllayer can be significantly larger than the pitch of the lamellae. Inthis instance, the lamellae of one block form parallel to the plane ofthe wafer on the exposed part of the patterned orientation controllayer, and the lamellac of the other block form perpendicular to theplane of the wafer on the unexposed portions of the patternedorientation control layer.

Thus, in another embodiment, a method of controlling the orientation ofmicrophase-separated domains and the directional alignment of themicrophase-separated domains in a block copolymer film, comprises (a)forming an orientation control layer comprising an epoxy-containingcycloaliphatic acrylic polymer over a surface of a substrate, (b)heating the substrate to crosslink the orientation control layer, (c)optionally, rinsing the orientation control layer with a solvent, (d)optionally, heating the substrate to remove residual solvent, (e)exposing the orientation control layer pattern-wise with actinicradiation, EUV, x-ray, or electron beam, to form a pattern of exposedand unexposed regions of the orientation control layer, (f) optionally,rinsing the patterned orientation control layer with a solvent, (g)optionally, heating the substrate having the patterned orientationcontrol layer to remove residual solvent, (h) forming a block copolymerassembly layer comprising a block copolymer having at least one blockthat forms microphase-separated domains on a surface of the patternedorientation control layer opposite the substrate, and (i) annealing thesubstrate to induce microphase-separated domains to form a pattern inthe block copolymer layer. In one specific embodiment, wherein themicrophase-separated domains are lamellae, and wherein a pitch of thepattern in the patterned orientation control layer is an order ofmagnitude larger than the pitch of lamellae, the lamellae form parallelto the plane of the substrate over the exposed region of the patternedorientation control layer, and form perpendicular to the plane of thesubstrate on the unexposed region of patterned orientation controllayer. In another specific embodiment, where the microphase-separateddomains are lamellae and a pitch of the pattern in the patternedorientation control layer is about the same as a pitch of the pattern inthe block copolymer layer, the exposed region is wetted by one domain ofthe block copolymer and the unexposed region is wetted by the otherdomain(s) of block copolymer, and the block copolymer forms a spatialreplica of the underlying patterned orientation control layer.

Articles can be prepared using the method described hereinabove. As oneexample, one or more aspects of the present invention can be included inan article of manufacture, e.g., one or more computer hardware productssuch as permanent or rewriteable data storage media such as hard disksreadable by a machine, employing, for instance, computer usable media.The media has embodied therein, for instance, computer readable programcode means for providing and facilitating the capabilities of thepresent invention. The article of manufacture can be included as a partof a computer system or sold separately. Other exemplary applicationsinclude fabrication of semiconductors including microprocessorsincluding those with memory caches, ASICs, and/or memory chips includingDRAM, SRAM, Flash, and the like.

The flow diagrams of the figures depicted herein are just examples.There may be many variations to these diagrams or the steps (oroperations) described therein without departing from the spirit of theinvention. For instance, the steps may be performed in a differingorder, or steps may be added, deleted or modified. All of thesevariations are considered a part of the claimed invention.

The invention is further described with respect to the examples, below.

EXAMPLES

The following examples are intended to provide those of ordinary skillin the art with a complete disclosure and description of how to prepareand use the compositions disclosed and claimed herein. Efforts have beenmade to ensure accuracy with respect to measured numbers, but allowanceshould be made for the possibility of errors and deviations. Unlessindicated otherwise, parts are parts by weight, temperature is in ° C.and pressure is at or near atmospheric. Epoxydicyclopentadienylmethacrylate was obtained from Elf-Atochem. Lamellae-formingpoly(styrene-b-methyl methacrylate) (18,000 g/mol/18,000 g/mol blocksizes, respectively) was obtained from Polymer Source. Cylinder-formingpoly(styrene-h-methyl methacrylate) (17,000 g/mol/38,000 g/mol blocksizes, respectively) was prepared by copolymerizing styrene and methylmethacrylate by a known procedure using the method of reversibleaddition-fragmentation chain transfer (RAFT) polymerization. PMMAprecursors with phenyl dithiobenzoate end groups were used as amacromolecular chain transfer agent for the RAFT polymerization. For afurther description of the method used, see Junwon Han, Chang Y. Ryu,Ho-Cheol Kim, Greg Breyta, and Hiroshi Ito, “Adsorption andFractionation of RAFT-polymerized PS-b-PMMA Block Copolymers for 2DLiquid Chromatography,” American Physical Society March Meeting AbstractN17.00003 (2007). Additionally, all the other chemicals and materialswere obtained commercially.

The following techniques and equipment were utilized in analysis of theexamples: ¹H and ¹³C NMR spectra were obtained at room temperature, andquantitative ¹³C NMR was run at room temperature in acetone-d₆ in aninverse-gated ¹H-decoupled mode using Cr(acac)₃ as a relaxation agent,on a Bruker AVANCE™ 400 NMR spectrometer. Thermo-gravimetric analysis(TGA) was performed at a heating rate of 5° C./min in N₂ on a TAInstrument Hi-Res TGA 2950 Thermogravimetric Analyzer. Differentialscanning calorimetry (DSC) was performed at a heating rate of 5° C./minon a TA Instruments DSC 2920 modulated differential scanningcalorimeter. Molecular weights were measured in tetrahydrofuran (THF) ona Waters Model 150 chromatograph relative to polystyrene standards. Filmthickness was measured on a Tencor ALPHA-STEP® 2000 or NanometricsNANOSPEC® film analysis system.

Contact angles were measured on an OCA video based contact angle systemfrom FDS Future Digital Scientific Corporation, using the sessile dropmethod. The advancing and receding contact angles were measured using atilting stage. The advancing and receding contact angles were measuredusing two different setups: tilting stage and/or captive drop. Unlessotherwise noted, all contact angles were measured using the tiltingstage. Reported static contact angles are calculated averages from 5 to10 measurements of a 2 μl ionized water drop. For advancing and recedingcontact angles, a 50 μl drop is placed on the substrate, the substrateis thereafter tilted until the droplet starts moving. The tilt angle(θ_(tilt)), θ_(adv) and θ_(rec) are measured just before the drop startsmoving. The presented numbers are calculated from and average of 3 to 5separate measurements.

General Synthesis Method for poly(epoxydicyclopentadienylmethacrylate-ran-styrene) polymers

Epoxydicyclopentadienyl methacrylate (EDCPDMA) (1.78 g, 17.1 mmol, 0.5eq.), styrene (4.0 g, 17.1 mmol, 0.5 eq.), and2,2′-azobis(2-methylpropionitrile) (AIBN) (0.224 g, 1.37 mmol, 0.04 eq.)were added to 20 ml, tetrahydrofuran in a 100 mL round-bottom flaskequipped with a reflux condenser and a nitrogen line. The solution wasdegassed by 3 pump-backfill cycles using nitrogen. The degassed solutionwas refluxed overnight (10 to 12 hours) under a nitrogen atmosphere. Thepolymers were precipitated into 800 mL hexanes, isolated on a glassfritted filter, washed with hexanes and dried overnight in vacuo at 70°C. Yield: 4.74 g (82%).

Polymers were synthesized according to the general procedure, using theappropriate ratios of monomers and initiator. For high styrene contentpolymers (>70%), methanol was used in place of hexanes as thenon-solvent for precipitations. Molecular weight (Mn) and polydispersitydata for the resulting polymers are shown in Table 1, below.

TABLE 1 Polymer EDCPDMA/styrene M_(n) [g/mol] PDI 1 100:0  14925 2.61 290:10 12212 1.93 3 80:20 8415 1.82 4 70:30 8192 1.58 5 60:40 6860 1.66 650:50 6209 1.62 7 40:60 6355 1.61 8 30:70 5819 1.51 9 20:80 5927 1.50 1010:90 6433 1.48

Formulation of poly(epoxydicyclopentadienyl methacrylate-ran-styrene)

Poly(epoxydicyclopentadienyl methacrylate-ran-styrene) was dissolved inpropylene glycol monomethyl ether acetate (PGMEA) and γ-butyrolactone(GBL) (solvent mixture ratios ranging from 100:0 to 70:30, depending onthe polymer) with N-hydroxyphthalimide triflate (10 wt % relative topolymer) as a thermal acid generator at a total solids of 1-2% by weightbased on the formulation. Other strong thermal and photoacid generatorswere also found to be sufficient to catalyze crosslinking, includingbis(4-t-butyl phenyl)iodonium triflate, bis(4-t-butyl phenyl)iodoniumperfluoro-1-butanesulfonate, bis(4-1-butyl phenyl)iodoniumperfluoro-1-octanesulfonate, bis(phenyl)iodonium hexafluoroantimonate,and N-hydroxy-5-norbornene-2,3-dicarboximideperfluoro-1-butanesulfonate.

Preparation of Crosslinked Films of poly(epoxydicyclopentadienylmethacrylate-ran-styrene)

Films were prepared by spin casting on silicon wafers at 2,000 to 3,000rpm as shown in FIG. 2. Film thickness was controlled by varying thesolids content of the casting solution and the spin rate duringspin-casting. The films were crosslinked in a two-step cure (130° C. for60 sec, and 200° C. for 120 sec). Crosslinking was verified by exposingthe cured films to puddles of organic solvent such as toluene or PGMEAfor 60 to 90 seconds and spin-drying. No film thickness loss or swellingwas observed. The roughness of the surfaces was characterized by AFM.Contact angle measurements (degrees) were used as a surrogate method fordetermining relative surface energies, in which a lower contact angleindicates a higher relative surface energy.

Orientation of PS-b-PMMA Domains on Neutral Crosslinked OrientationControl Layers

Solutions of PS-b-PMMA were cast onto the crosslinked neutralorientation control layers from PGMEA and annealed at 200° C. for timesvarying from 1 minute to 18 hours. Orientation of the PS and PMMAdomains was observed by atomic force microscopy.

Table 2 shows the orientation of PS-b-PMMA block copolymers that formlamellae (La) and cylinders (Cy) on crosslinked orientation controllayers of the composition described in Table 1 compositions as afunction of annealing time. The composition of the orientation controllayer polymer, contact angle (CA, in degrees), and annealing time aregiven. Perpendicular lamellae or cylinders are formed as indicated bythe symbol “⊥”; where fewer than 100% of such features are formed, theamount is indicated as a percentage. The total solids content of theformulation is 1% or 2% by weight, as indicated.

TABLE 2 La La La La La Cy Cy EDCPDMA/ 1% 1% 2% 2% 2% 1% 1% Styrene CA 1min 6 hr 1 min 6 hr 18 hr 1 min 10 min 100:0 63.6 ⊥ ⊥ ⊥ <50%⊥  ~0%⊥~50%⊥ <50%⊥ 90:10 65.7 ⊥ ⊥ ⊥ ~70%⊥ ~50%⊥ ~50%⊥ <50%⊥ 80:20 67.1 ⊥ ⊥ ⊥ ⊥⊥ ~70%⊥ <50%⊥ 70:30 68.4 ⊥ ⊥ ⊥ ⊥ ⊥ ~70%⊥ ~70%⊥ 60:40 71.2 ⊥ ⊥ ⊥ ⊥ ⊥~90%⊥ ~70%⊥ 50:50 73.6 ⊥ ⊥ ⊥ ⊥ ⊥ ~90%⊥ ~70%⊥ 40:60 78 ⊥ ⊥ ⊥ ⊥ ⊥ ⊥ >90%⊥30:70 78.3 ⊥ ⊥ ⊥ ⊥ ⊥ ⊥ ⊥

In a further example, as shown in FIG. 8B and FIG. 8C, the crosslinkedorientation control layer was patterned by a photopatterning method toprovide developed, orientation control layer-free regions on thesubstrate, and a lamellae-forming block copolymer as describedhereinabove was coated on the substrate and processed as above. In theAFM image of FIG. 8B, it can be seen that the regions of the blockcopolymer layer disposed over the regions of the substrate free of theorientation control layer have parallel orientation of the lamellae.(i.e., no lamellar pattern is visible). In the AFM image of FIG. 8C, itcan be seen that the regions of the block copolymer layer disposed overthe regions of the substrate having the orientation control layerpattern have perpendicular orientation of the lamellae (i.e., thelamellar pattern is visible).

In a further example, as shown in FIG. 9B, the orientation control layerwas patterned by direct write e-beam method, and a lamellac-formingblock copolymer as described hereinabove was coated on the substrate andprocessed as above. In the AFM image of FIG. 9B, it can be seen that thepattern of lamellae formed in the block copolymer layer coincides withthe pattern imaged by e-beam in the orientation control layer.

While the preferred embodiment to the invention has been described, itwill be understood that those skilled in the art, both now and in thefuture, may make various improvements and enhancements which fall withinthe scope of the claims which follow. These claims should be construedto maintain the proper protection for the invention first described.

1. A method of controlling the orientation of microphase-separateddomains in a block copolymer film, comprising: (a) forming anorientation control layer comprising an epoxy-containing cycloaliphaticacrylic polymer over a surface of a substrate, (b) irradiating and/orheating to crosslink the orientation control layer, (c) forming a blockcopolymer assembly layer comprising a block copolymer that formsmicrophase-separated domains upon forming the block copolymer assemblylayer, on a surface of the orientation control layer opposite thesubstrate, and (d) removing at least one microphase-separated domain togenerate a topographical pattern.
 2. The method of claim 1, whereinforming the orientation control layer in (a) comprises: applying a firstcomposition comprising the epoxy-containing cycloaliphatic acrylicpolymer and a solvent on a surface of a substrate by a film depositionprocess.
 3. The method of claim 2, wherein the applied epoxy-containingcycloaliphatic acrylic polymer is optionally baked at a temperature of70 to 150° C. for at least 20 seconds.
 4. The method of claim 2, whereinthe first composition comprises: a base polymer comprising Formula (1),Formula (2), or a combination comprising at least one of the foregoingbase polymers,

wherein, in Formulas (1) and (2) R₁, R₂, R₅, R_(5′) and R₆ areindependently H, F, CF₃, or CH₃, R₃ is a substituted or unsubstitutedphenyl, naphthyl, or anthracyl group, R₄ and R₈ are independentlymonocyclic or polycyclic C₆₋₁₂ epoxy-containing groups, R₇ and R_(7′)are each independently a C₁₋₂₀ aromatic group or C₁₋₂₀ aliphatic group,and at least one of R₅ and R_(5′), or R₇ and R_(7′) are not identical;and in Formulas (1) and (2), x and y are independently 0 to 98%, z is 2to 100%, the sum of monomer mole percentages x+y+z is at least 85%, andthe ratio of the mole percentages of x+y to z is 0:100 to 98:2; and anacid generator comprising a thermal acid generator, photoacid generator,or a combination of thermal acid generator and photoacid generator. 5.The method of claim 4, wherein the first composition further comprisesan additive comprising a surfactant, a quencher, a hardener, acrosslinker, a chain extender, or a combination comprising at least oneof the foregoing additives.
 6. The method of claim 1, wherein in (b),heating comprises baking the substrate having the orientation controllayer at a temperature of 100 to 250° C. for at least 30 seconds.
 7. Themethod of claim 1, wherein the block copolymer comprises blockscomprising one or more monomers, at least two blocks in the blockcopolymer are compositionally non-identical, and the block copolymer isa diblock copolymer, triblock copolymer, or multiblock copolymer.
 8. Themethod of claim 7, comprising baking the substrate having the blockcopolymer and orientation control layers is done: at a temperature of 70to 150° C. for at least 20 seconds.
 9. The method of claim 7, whereinthe blocks comprise monomers comprising C₂₋₃₀ olefinic monomers,(meth)acrylate monomers derived from C₁₋₃₀ alcohols, or a combinationcomprising at least one of the foregoing monomers.
 10. The method ofclaim 1, wherein forming the block copolymer assembly layer comprises:applying a second composition comprising the block copolymer and acasting solvent, to a surface of the orientation control layer oppositethe substrate by a process comprising spin-casting, dip-coating, doctorblading, or spray dispense.
 11. The method of claim 10, wherein thesecond composition comprises at least one additional component selectedfrom the group consisting of homopolymers, copolymers, crosslinkablepolymers; small molecules, surfactants, photoacid generations, thermalacid generators, quenchers, hardeners, cross-linkers, chain extenders,and a combination comprising at least one of the foregoing; wherein oneor more of the additional components co-assemble with themicrophase-separated domains of the block copolymer to form the blockcopolymer assembly layer.
 12. The method of claim 1 wherein theorientation control layer is disposed on a surface of layered film stackcomprising: a substrate, a pattern transfer layer disposed on a surfaceof the substrate, and a hardmask disposed on a surface of the patterntransfer layer, wherein the orientation control layer is in contact withan exposed surface of the hardmask.
 13. The method of claim 12, furthercomprising pattern transfer from the topographical pattern in the blockcopolymer assembly layer to the orientation control layer by a reactiveion etch process to generate a topographic pattern in the orientationcontrol layer, followed by pattern transfer from the patternedorientation control layer to the hardmask by a hardmask etch.
 14. Themethod of claim 1, wherein the block copolymer of the block copolymerassembly layer comprises a block comprising inorganic-containingmonomers comprising silicon-containing monomers, germanium-containingmonomers, or metal-containing monomers; or wherein the block copolymerassembly layer comprises, in addition to the block copolymer,inorganic-containing polymers or inorganic-containing molecules whichassemble with the block copolymer to form the microphase-separateddomains of the block copolymer assembly layer.
 15. The method of claim1, further comprising after (b) and before (c): rinsing the orientationcontrol layer with a solvent; and heating the substrate to removeresidual solvent.
 16. The method of claim 1, further comprisingannealing the substrate to induce pattern formation in the blockcopolymer layer, wherein annealing the substrate is carried out at 80 to300° C. for a time of 30 seconds to 48 hours.
 17. The method of claim 5wherein the thermal and/or photoacid generator is present in an amountof 0.01 to 10 wt % based on the total weight of the first composition,the additive is present in an amount of 0.01 to 10 wt % of the totalweight of the first composition, and the total solids of the firstcomposition comprising base polymer, thermal acid generator and/orphoto-acid generator, and additive is 0.5 to 30 wt % based on the totalweight of the first composition including casting solvent.
 18. Themethod of claim 1, wherein the microphase-separated domains arecylindrical microphase-separated domains oriented perpendicular to thesurface of the orientation control layer, or wherein themicrophase-separated domains are lamellar domains oriented perpendicularto the surface of the orientation control layer.
 19. The method of claim1, further comprising pattern transfer from the topographic pattern inthe block copolymer assembly layer to the substrate by a reactive ionetch process.
 20. A method of controlling the orientation ofmicrophase-separated domains in specific areas of a substrate coatedwith a block copolymer film, comprising: (a) forming an orientationcontrol layer comprising an epoxy-containing cycloaliphatic acrylicpolymer over a surface of a substrate, (b) exposing the orientationcontrol layer pattern-wise with actinic radiation, EUV, or electronbeam, to form a pattern of exposed and unexposed regions of theorientation control layer, (c) heating the substrate to crosslink theorientation control layer in the exposed regions, (d) removinguncrosslinked orientation control layer material in the unexposedregions with a solvent to uncover the surface of the substrate in theunexposed regions, (e) optionally, heating the substrate having thepatterned crosslinked orientation control layer to remove residualsolvent, (f) forming a block copolymer assembly layer comprising a blockcopolymer that forms microphase-separated domains, on a surface of thepatterned crosslinked orientation control layer opposite the substrate,and (g) optionally, annealing the substrate to induce pattern formationin the block copolymer layer, wherein lamellae form perpendicular to theplane of the substrate over the crosslinked orientation control layer,and wherein lamellae form parallel to the plane of the substrate overthe uncovered surface of the substrate.
 21. The method of claim 20,further comprising removing at least one microphase-separated domain togenerate a topographical pattern, followed by pattern transfer from thetopographic pattern to the substrate by a reactive ion etch process. 22.A method of controlling the orientation of microphase-separated domainsand the directional alignment of the microphase-separated domains in ablock copolymer film, comprising: (a) forming an orientation controllayer comprising an epoxy-containing cycloaliphatic acrylic polymer overa surface of a substrate, (b) heating the substrate to crosslink theorientation control layer, (c) optionally, rinsing the orientationcontrol layer with a solvent, (d) optionally, heating the substrate toremove residual solvent, (e) exposing the orientation control layerpattern-wise with actinic radiation, EUV, x-ray, or electron beam, toform a pattern of exposed and unexposed regions of the orientationcontrol layer, (f) optionally, rinsing the patterned orientation controllayer with a solvent, (g) optionally, heating the substrate having thepatterned orientation control layer to remove residual solvent, (h)forming a block copolymer assembly layer comprising a block copolymerhaving at least one block that forms microphase-separated domains on asurface of the patterned orientation control layer opposite thesubstrate, and (i) annealing the substrate to inducemicrophase-separated domains to form a pattern in the block copolymerlayer, wherein the microphase-separated domains are lamellae, andwherein when a pitch of the pattern in the patterned orientation controllayer is at least 200% larger than the pitch of lamellae, the lamellaeform parallel to the plane of the substrate over the exposed region ofthe patterned orientation control layer, and form perpendicular to theplane of the substrate on the unexposed region of patterned orientationcontrol layer.
 23. The method of claim 22, further comprising removingat least one microphase-separated domain to generate a topographicalpattern, followed by pattern transfer from the topographic pattern tothe substrate by a reactive ion etch process.
 24. A method ofcontrolling the orientation of microphase-separated domains and thedirectional alignment of the microphase-separated domains in a blockcopolymer film, comprising: (a) forming an orientation control layercomprising an epoxy-containing cycloaliphatic acrylic polymer over asurface of a substrate, (b) heating the substrate to crosslink theorientation control layer, (c) optionally, rinsing the orientationcontrol layer with a solvent, (d) optionally, heating the substrate toremove residual solvent (e) exposing the orientation control layerpattern-wise with actinic radiation, EUV, x-ray, or electron beam, toform a pattern of exposed and unexposed regions of the orientationcontrol layer, (f) optionally, rinsing the patterned orientation controllayer with a solvent, (g) optionally, heating the substrate having thepatterned orientation control layer to remove residual solvent, (h)forming a block copolymer assembly layer comprising a block copolymerhaving at least one block that forms microphase-separated domains on asurface of the patterned orientation control layer opposite thesubstrate, and (i) annealing the substrate to inducemicrophase-separated domains to form a pattern in the block copolymerlayer, wherein the microphase-separated domains are lamellac, andwherein when a pitch of the pattern in the patterned orientation controllayer is about the same as a pitch of the pattern in the block copolymerlayer, the exposed region is wetted by one domain of the block copolymerand the unexposed region is wetted by the other domain(s) of blockcopolymer, and the block copolymer forms a spatial replica of theunderlying patterned orientation control layer.
 25. The method of claim24, further comprising removing at least one microphase-separated domainto generate a topographical pattern, followed by pattern transfer fromthe topographic pattern to the substrate by a reactive ion etch process.